CN112374956B - Process for the preparation of 1-butene and 1-hexene - Google Patents
Process for the preparation of 1-butene and 1-hexene Download PDFInfo
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- CN112374956B CN112374956B CN202011311578.0A CN202011311578A CN112374956B CN 112374956 B CN112374956 B CN 112374956B CN 202011311578 A CN202011311578 A CN 202011311578A CN 112374956 B CN112374956 B CN 112374956B
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- butene
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 title claims abstract description 128
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 56
- 230000008569 process Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 130
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000005977 Ethylene Substances 0.000 claims abstract description 102
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 238000005829 trimerization reaction Methods 0.000 claims abstract description 33
- 238000006471 dimerization reaction Methods 0.000 claims abstract description 22
- 238000004904 shortening Methods 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims description 17
- 238000006384 oligomerization reaction Methods 0.000 claims description 17
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 14
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 150000003233 pyrroles Chemical class 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- NPDIDUXTRAITDE-UHFFFAOYSA-N 1-methyl-3-phenylbenzene Chemical group CC1=CC=CC(C=2C=CC=CC=2)=C1 NPDIDUXTRAITDE-UHFFFAOYSA-N 0.000 claims description 6
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012429 reaction media Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical compound CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 3
- ALLIZEAXNXSFGD-UHFFFAOYSA-N 1-methyl-2-phenylbenzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1 ALLIZEAXNXSFGD-UHFFFAOYSA-N 0.000 claims description 3
- GVEDOIATHPCYGS-UHFFFAOYSA-N 1-methyl-3-(3-methylphenyl)benzene Chemical group CC1=CC=CC(C=2C=C(C)C=CC=2)=C1 GVEDOIATHPCYGS-UHFFFAOYSA-N 0.000 claims description 3
- QCWXDVFBZVHKLV-UHFFFAOYSA-N 1-tert-butyl-4-methylbenzene Chemical compound CC1=CC=C(C(C)(C)C)C=C1 QCWXDVFBZVHKLV-UHFFFAOYSA-N 0.000 claims description 3
- MRIWRLGWLMRJIW-UHFFFAOYSA-N benzyl(trimethyl)silane Chemical compound C[Si](C)(C)CC1=CC=CC=C1 MRIWRLGWLMRJIW-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 3
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 claims description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 229960002809 lindane Drugs 0.000 claims description 2
- WTWWXOGTJWMJHI-UHFFFAOYSA-N perflubron Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)Br WTWWXOGTJWMJHI-UHFFFAOYSA-N 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 238000013268 sustained release Methods 0.000 claims description 2
- 239000012730 sustained-release form Substances 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000003340 retarding agent Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 230000006698 induction Effects 0.000 abstract description 8
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 230000000536 complexating effect Effects 0.000 abstract description 5
- 239000004711 α-olefin Substances 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 53
- 238000007789 sealing Methods 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 19
- 238000005516 engineering process Methods 0.000 description 14
- 239000007791 liquid phase Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- 239000007790 solid phase Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 12
- -1 polyethylene Polymers 0.000 description 9
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 8
- MTWOPAXLOPAHRI-UHFFFAOYSA-N 2-ethylhexane-1,3-diol;titanium Chemical compound [Ti].CCCC(O)C(CC)CO.CCCC(O)C(CC)CO.CCCC(O)C(CC)CO.CCCC(O)C(CC)CO MTWOPAXLOPAHRI-UHFFFAOYSA-N 0.000 description 8
- 101150065749 Churc1 gene Proteins 0.000 description 8
- 102100038239 Protein Churchill Human genes 0.000 description 8
- 238000005086 pumping Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000001502 supplementing effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of 1-butene and 1-hexene, which couples the rates of ethylene dimerization and ethylene trimerization, and comprises a process of shortening the time of ethylene dimerization to generate 1-butene and a process of increasing the time of ethylene trimerization to generate 1-hexene. In the invention, ethylene is dimerized to generate 1-butene, and the catalyst composition is a binary catalytic system, so that the complexing process is cancelled, the induction period is greatly shortened, and the reaction retention time is reduced; in the invention, ethylene is trimerized to generate 1-hexene for reaction, and an inert effect slow-release agent component is added into a catalytic system, so that the reaction induction period can be greatly prolonged, and the reaction retention time can be prolonged; therefore, the reaction rate difference of 1-butene produced by ethylene dimerization and 1-hexene produced by ethylene trimerization is balanced, and two alpha-olefins can be produced by one set of reaction device.
Description
Technical Field
The invention relates to the field of preparing alpha-olefin by ethylene oligomerization, in particular to a novel ethylene oligomerization method for producing 1-butene and 1-hexene by flexible operation.
Background
The 1-butene and the 1-hexene are main comonomers for producing Linear Low Density Polyethylene (LLDPE) and High Density Polyethylene (HDPE), short and side chain structures provided by the 1-butene and the 1-hexene as tie molecules can endow stronger bonding force among polyethylene lamella crystals, and obviously improve the mechanical properties of the polyethylene product, such as tensile strength, impact strength, tear resistance and the like. In industrial processes, it is generally necessary to add from 1 to 10% of comonomer to produce copolymerized polyethylene.
At present, the industrial production technologies of 1-butene and 1-hexene can be roughly divided into three types, the first type is to obtain polymerization-grade 1-butene or 1-hexene from cracking C4 or Fischer-Tropsch olefins and other mixed raw materials through separation and purification, and the representative technologies are as follows: the 1-butene technology of UOP company and the coal dry distillation technology of Sasol company have the advantages of low raw material and processing cost and the defects of high dependence on raw material resources, high impurity content of products and poor quality. The second type is the traditional technology for preparing alpha-olefin by ethylene oligomerization, which takes ethylene as raw material to produce series alpha-olefin and then separates 1-butene and 1-hexene from the intermediate material, and the representative technology is as follows: the one-step process of Chevron company, the two-step process of INEOS company, the SHOP process of Shell company, the SABLIN process of Sabic company and the like have the advantages of wide application range, capability of simultaneously producing 1-butene and 1-hexene, and the defects that the total selectivity of the 1-butene and the 1-hexene is low, the yield ratio of two comonomers cannot be flexibly adjusted, the single set of capacity of the device is large, and the energy consumption for operation is high. The third type is high-selectivity ethylene oligomerization technology, which refers to the technology of 1-butene synthesis through ethylene dimerization, 1-hexene synthesis through ethylene trimerization, 1-octene synthesis through ethylene tetramerization and the like, and the representative technologies include ethylene dimerization technology of Axens company, ethylene trimerization technology of Phillips company, ethylene trimerization technology of medium petroleum and the like.
Ethylene dimerization to 1-butene catalysts are generally multi-component catalytic systems consisting of a transition metal, a ligand and an aluminum alkyl. A three-way catalytic system such as IFP (general formula Ti (OR)) 4 OR Ti (OR') 4 Titanium alkoxide OR aryloxide, aluminum compound and Lewis base type additive and quaternary catalyst system (general formula Ti (OR)) 4 Titanates, ether modifiers, aluminoxanes and also with the further aluminum compound). A large number of researches show that the ternary/quaternary catalytic system needs to be complexed in advance, and the existence of the complexing process prolongs the reaction induction period, influences the performance of the catalyst efficiency and ensures that the reaction retention time (generally more than 4 hours) cannot be shortened.
The catalyst for trimerization of ethylene to produce 1-hexene is usually a multi-component catalyst system consisting of a main catalyst, a ligand, an auxiliary catalyst and an auxiliary agent. Such as Phillips (chromium-containing compound a, pyrrole-containing compound b, alkyl metal c and halogen-containing compound d) and China oil and gas group (chromium-containing compound a, P and/or N-containing ligand b, alkyl aluminum c and promoter d). A large number of researches show that the components of the ethylene trimerization catalytic system are fully contacted, namely, an active intermediate is quickly formed, so that the rapid reaction is started, and the catalyst is inactivated after about 0.5 hour.
Because the reaction rate difference between the ethylene dimerization reaction and the ethylene trimerization reaction is too large, the switching reaction can not be realized in the reactor with the same volume, so that no device capable of flexibly switching to produce 1-butene and 1-hexene with high selectivity exists in the world at present. In the traditional process of synthesizing 1-butene by ethylene dimerization, because complexing is needed among the adopted multi-component catalysts to further form an active intermediate, the reaction rate at the initial stage of the reaction is influenced by the process, the CN105233868 and CN105828941 are mentioned, and the initial induction period of the reaction is too long due to the complexing process, so that the reaction time is generally more than 4 hours and cannot be shortened. The traditional method for synthesizing 1-hexene by trimerizing ethylene is a rapid reaction, when catalytic components are fully contacted, an active intermediate is rapidly formed, and then the reaction is started, after about 0.5 hour of reaction, the catalyst is deactivated, and the deactivated catalyst cannot be subjected to the trimerization of ethylene, which is mentioned in CN102107146A and CN 1872416. Therefore, aiming at the huge demand of the current polyethylene device on 1-butene and 1-hexene, the technology for realizing ethylene oligomerization and flexibly switching to produce high-quality 1-butene and 1-hexene comonomers by balancing the reaction rate has important economic and practical values and scientific research significance.
Disclosure of Invention
The invention aims to develop a novel ethylene oligomerization method for producing 1-butene and 1-hexene through flexible operation, which realizes the speed coupling of ethylene dimerization and ethylene trimerization, and comprises a novel method for shortening the time of ethylene dimerization to generate 1-butene and a novel method for increasing the time of ethylene trimerization to generate 1-hexene.
To achieve the above objects, the present invention provides a process for producing 1-butene and 1-hexene by coupling the rates of dimerization of ethylene and trimerization of ethylene, comprising a process for shortening the time for dimerization of ethylene to produce 1-butene and a process for increasing the time for trimerization of ethylene to produce 1-hexene.
The invention relates to a method for preparing 1-butene and 1-hexene, wherein the process for shortening the time of ethylene dimerization reaction to generate 1-butene comprises the following steps: premixing a cocatalyst and a main catalyst or respectively adding the cocatalyst and the main catalyst into an oligomerization reactor containing a reaction medium, controlling the reaction temperature, introducing an ethylene monomer and keeping the reaction pressure to carry out oligomerizationPreparing 1-butene; the main catalyst is selected from the general formula MX 2 At least one of the metal compounds of (1).
The invention relates to a preparation method of 1-butene and 1-hexene, wherein the process for increasing the time for generating 1-hexene through ethylene trimerization reaction comprises the following steps: premixing or respectively adding a cocatalyst, a main catalyst, a ligand, an auxiliary agent and an efficiency slow-release agent into an oligomerization reactor containing a reaction medium, controlling the reaction temperature, introducing an ethylene monomer and keeping the reaction pressure, and carrying out oligomerization to prepare 1-hexene; the efficacy slow-release agent is at least one selected from silanes, imines and acetals.
The invention relates to a preparation method of 1-butene and 1-hexene, wherein, the main catalyst is selected from one or more of main group or transition metal compounds, preferably one or more of main group I/II/III metal compounds and transition metal compounds of subgroup II/IV/V/VI/VIII, preferably the compound formula is M (OCHRXCHRO) 2 。
The invention relates to a method for preparing 1-butene and 1-hexene, wherein the main catalyst is Ti [ OCHR ] 1 CHR 2 CHR 3 O] 2 Wherein R1, R2, R3 are hydrogen atoms, or straight or branched chain alkyl groups of 1 to 20 carbon atoms, or aryl groups substituted or not with alkyl, aryl or aralkyl groups containing 2 to 30 carbon atoms.
The invention relates to a preparation method of 1-butene and 1-hexene, wherein, the efficacy slow release agent is selected from one or more of alkane, cyclane and aryl compound.
In the preparation method of the 1-butene and 1-hexene, the efficacy slow release agent is one or more of aryl compounds, preferably one or more of benzene, toluene, ethylbenzene, propylbenzene, 3,3' -dimethylbiphenyl, phenylsilane, 2-ethylaniline, N-ethylaniline, 2-methylbiphenyl, 3-methylbiphenyl, benzyltrimethylsilane and p-tert-butyltoluene.
The preparation method of the 1-butene and the 1-hexene comprises the step of premixing the main catalyst and the efficiency sustained-release agent in advance.
The preparation method of the 1-butene and the 1-hexene comprises the steps of premixing at the temperature of 0-50 ℃ under the pressure of 0-2 MPa, wherein the premixing molar ratio of the main catalyst to the efficacy slow-release agent is 1 (1-10).
The invention relates to a preparation method of 1-butene and 1-hexene, wherein a cocatalyst is selected from one or more alkyl aluminum compounds, preferably one or more of trimethyl aluminum, triethyl aluminum and triisobutyl aluminum.
The invention relates to a preparation method of 1-butene and 1-hexene, wherein, the ligand is selected from one or more of pyrrole compounds, preferably one or more of pyrrole, 1-methylpyrrole, 2,5-dimethylpyrrole; the auxiliary agent is selected from one or more of halogenated alkane compounds, preferably one or more of tetrabromoethane, 1-bromoheptadecafluorooctane and hexachlorocyclohexane.
The preparation method of the 1-butene and the 1-hexene comprises the steps of reacting at the temperature of 10-120 ℃ and under the pressure of 1-10 MPa.
The preparation method of the 1-butene and the 1-hexene comprises the steps of reacting at the temperature of 30-150 ℃ and under the pressure of 1-10 MPa.
The invention relates to a preparation method of 1-butene and 1-hexene, wherein the molar ratio of a cocatalyst to a main catalyst is (3-15): 1.
The invention relates to a preparation method of 1-butene and 1-hexene, wherein the molar ratio of a main catalyst, a ligand, an auxiliary catalyst, an auxiliary agent and an efficacy slow-release agent is 1 (3-6) to (50-150) to (10-20) to (1-10).
The invention can also be detailed as follows:
ethylene dimerization to 1-butene reaction:
the novel method for shortening the time of generating 1-butene by ethylene dimerization reaction comprises the following steps: premixing a cocatalyst and a main catalyst or respectively adding the cocatalyst and the main catalyst into an oligomerization reactor containing a reaction medium, controlling a proper reaction temperature, introducing an ethylene monomer and keeping the reaction pressure to perform oligomerization to prepare 1-butene; the general formula of the main catalyst is Ti [ OCHR ] 1 CHR 2 CHR 3 O] 2 Wherein R1, R2 and R3 can be hydrogen atoms or straight chain or branched chain alkyl groups with 1 to 20 carbon atoms or can not contain 2Alkyl, aryl or aralkyl substituted aryl of 30 carbon atoms. The specific structure of the main catalyst is as follows:
the main catalyst has a specific Ti-O double-ring structure, can strengthen the limiting capacity, protect active sites, solve the problems of disordered control of activation and catalysis and excessive reduction of metals, shorten the reaction induction period and reduce the reaction retention time while ensuring the catalytic activity and the selectivity of 1-butene, and achieve the aim of balancing the reaction rate of 1-butene and the reaction rate of 1-hexene.
Ethylene trimerization to 1-hexene reaction:
the new method for increasing the time for generating 1-hexene through ethylene trimerization reaction comprises the following steps: adding a cocatalyst, a main catalyst, a ligand, an auxiliary agent and an efficiency slow-release agent into an oligomerization reactor containing a reaction medium, wherein the main catalyst and the efficiency slow-release agent need to be premixed in advance, controlling a proper reaction temperature, introducing an ethylene monomer and keeping the reaction pressure, and carrying out oligomerization to prepare 1-hexene; the efficiency slow release agent is preferably one or more of aryl compounds, and can be further preferably one or more selected from benzene, toluene, ethylbenzene, propylbenzene, 3,3' -dimethylbiphenyl, phenylsilane, 2-ethylaniline, N-ethylaniline, 2-methylbiphenyl, 3-methylbiphenyl, benzyltrimethylsilane and p-tert-butyltoluene.
The premixing temperature of the main catalyst and the efficiency slow-release agent is 0-50 ℃, the premixing pressure is 0-2 MPa, and the premixing molar ratio of the main catalyst to the efficiency slow-release agent is 1:1-1.
The catalyst efficiency slow release technology is to treat the 1-hexene catalyst by an inert active site protective agent to shield the active site of the catalyst, so as to achieve the purpose of keeping the activity of the catalyst under harsh working conditions. The efficiency slow release agent has chemical inertness, can be gradually replaced after contacting with the catalyst and ethylene, does not influence reaction and separation, and simultaneously has the advantages of prolonging the reaction induction period and increasing the reaction residence time due to the slow replacement process, thereby achieving the aim of balancing the 1-butene reaction rate and the 1-hexene reaction rate.
The invention has the following advantages:
(1) In the invention, ethylene is dimerized to generate 1-butene for reaction, and the catalyst composition is a binary catalytic system, so that compared with a foreign multi-element catalytic system, a complexing process is cancelled, the induction period is greatly shortened, and the reaction retention time is reduced; meanwhile, side reactions caused by uneven complexation of the multicomponent components are avoided;
(2) In the invention, ethylene is trimerized to generate 1-hexene for reaction, and an inert effect slow-release agent component is added into a catalytic system, so that the reaction induction period can be greatly prolonged, and the reaction retention time can be prolonged;
(3) The reaction rate difference of 1-butene produced by ethylene dimerization and 1-hexene produced by ethylene trimerization is balanced, and two kinds of alpha-olefin can be produced by one set of reaction device.
Drawings
FIG. 1 is a schematic diagram of increasing the time for ethylene trimerization to produce 1-hexene.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
Method for dimerizing ethylene to 1-butene:
example 1
Heating a high-pressure reaction kettle to a certain temperature, vacuumizing, regulating the temperature to 50 ℃ after ensuring that the used reaction kettle is completely dried, sealing the reaction kettle, and adding N 2 Replacing gas in the kettle for several times, pumping and discharging ethylene gas for several times, and sequentially injecting cyclohexane solvent and tetra (2-ethyl-1,3-hexanediol) titanium (structural formula: ti [ OCH ] 2 CHCH 2 CH 3 CHCH 2 CH 2 CH 3 O] 2 ) And triethylaluminum, wherein the molar ratio of triethylaluminum to tetrakis (2-ethyl-1,3-hexanediol) titanium was 1:1, and ethylene was fed. Continuously reacting for a period of time at a preset reaction temperature of 50 ℃ and a reaction pressure of 2.5MPa, quantitatively collecting gas-phase products by using a wet gas flowmeter and a gas collecting bag after the reaction is finished, collecting liquid-phase products by using a flask, collecting solid-phase products by using a sealing bag, and analyzing and calculating the obtained products respectively.
Example 2
Heating a high-pressure reaction kettle to a certain temperature, vacuumizing, regulating the temperature to 50 ℃ after ensuring that the used reaction kettle is completely dried, sealing the reaction kettle, and adding N 2 Replacing gas in the kettle for several times, pumping and discharging ethylene gas for several times, and sequentially injecting hexane solvent and tetra (2-ethyl-1,3-hexanediol) titanium (structural formula: ti [ OCH ] 2 CHCH 2 CH 3 CHCH 2 CH 2 CH 3 O] 2 ) And triethylaluminum, wherein the molar ratio of triethylaluminum to tetrakis (2-ethyl-1,3-hexanediol) titanium was 1:1, and ethylene was fed. Continuously reacting for a period of time at a preset reaction temperature of 50 ℃ and a reaction pressure of 2.5MPa, quantitatively collecting gas-phase products by using a wet gas flowmeter and a gas collecting bag after the reaction is finished, collecting liquid-phase products by using a flask, collecting solid-phase products by using a sealing bag, and analyzing and calculating the obtained products respectively.
Example 3
Heating a high-pressure reaction kettle to a certain temperature, vacuumizing, regulating the temperature to 50 ℃ after ensuring that the used reaction kettle is completely dried, sealing the reaction kettle, and adding N 2 Replacing gas in the kettle for several times, pumping ethylene gas for several times, sequentially injecting cyclohexane solvent and tetra (2-ethyl-1,3-hexanediol) titanium (formula: ti [ OCH ] 2 CHCH 2 CH 3 CHCH 2 CH 2 CH 3 O] 2 ) And triethylaluminum, wherein the molar ratio of triethylaluminum to tetrakis (2-ethyl-1,3-hexanediol) titanium was 2:1, and ethylene was fed. Continuously reacting for a period of time at a preset reaction temperature of 50 ℃ and a reaction pressure of 2.5MPa to obtain a reaction mixtureAnd after that, quantitatively collecting the gas-phase product by using a wet gas flowmeter and a gas collecting bag, collecting the liquid-phase product by using a flask, collecting the solid-phase product by using a sealing bag, and analyzing and calculating the obtained products respectively.
Example 4
Heating a high-pressure reaction kettle to a certain temperature, vacuumizing, regulating the temperature to 50 ℃ after ensuring that the used reaction kettle is completely dried, sealing the reaction kettle, and adding N 2 Replacing gas in the kettle for several times, pumping and discharging ethylene gas for several times, and sequentially injecting cyclohexane solvent and tetra (2-ethyl-1,3-hexanediol) titanium (structural formula: ti [ OCH ] 2 CHCH 2 CH 3 CHCH 2 CH 2 CH 3 O] 2 ) And triethylaluminum, wherein the molar ratio of triethylaluminum to tetrakis (2-ethyl-1,3-hexanediol) titanium was 2:1, and ethylene was fed. Continuously reacting for a period of time at a preset reaction temperature of 50 ℃ and a reaction pressure of 2.0MPa, quantitatively collecting gas-phase products by using a wet gas flowmeter and a gas collecting bag after the reaction is finished, collecting liquid-phase products by using a flask, collecting solid-phase products by using a sealing bag, and analyzing and calculating the obtained products respectively.
Comparative example 1
Heating a high-pressure reaction kettle to a certain temperature, vacuumizing, regulating the temperature to 50 ℃ after ensuring that the used reaction kettle is completely dried, sealing the reaction kettle, and adding N 2 Replacing gas in the kettle for several times, pumping and discharging ethylene gas for several times, injecting cyclohexane solvent, tetrabutyl titanate, triethyl aluminum and THF into the kettle, wherein the molar ratio of triethyl aluminum to tetrabutyl titanate is 1:1, and introducing ethylene. Continuously reacting for a period of time at a preset reaction temperature of 50 ℃ and a reaction pressure of 2.5MPa, quantitatively collecting a gas-phase product by using a wet gas flowmeter and a gas collecting bag after the reaction is finished, collecting a liquid-phase product by using a flask, collecting a solid-phase product by using a sealing bag, and analyzing and calculating the obtained products respectively.
Comparative example 2
Heating the high-pressure reaction kettle to a certain temperature, and then vacuumizing to ensure the temperatureAfter the used reaction kettle is completely dried, the temperature is adjusted to 50 ℃, the reaction kettle is sealed, and N is used 2 Replacing gas in the kettle for several times, pumping and discharging ethylene gas for several times, injecting cyclohexane solvent, tetrabutyl titanate, triethyl aluminum and THF into the kettle, wherein the molar ratio of triethyl aluminum to tetrabutyl titanate is 2:1, and introducing ethylene. Continuously reacting for a period of time at a preset reaction temperature of 50 ℃ and a reaction pressure of 2.0MPa, quantitatively collecting a gas-phase product by using a wet gas flowmeter and a gas collecting bag after the reaction is finished, collecting a liquid-phase product by using a flask, collecting a solid-phase product by using a sealing bag, and analyzing and calculating the obtained products respectively.
TABLE 1 results of ethylene dimerization examples and comparative examples are summarized
The method for generating 1-hexene by ethylene trimerization comprises the following steps:
example 5
(1) The premixing method of the main catalyst and the efficiency slow-release agent comprises the following steps: taking the cleaned and dried pressure-resistant container, opening a valve, and adding N 2 Adding an efficacy slow-release agent and a main catalyst into the reactor in sequence under protection, wherein the premixed molar ratio of the main catalyst to the efficacy slow-release agent is 1:1, closing a valve, heating to 30 ℃, and supplementing N into the reactor 2 Stirring the mixture for 60min to 0.5MPa, and marking the mixture as a complex a of the main catalyst and the efficacy slow-release agent.
(2) The ethylene trimerization reaction method comprises the following steps: heating the cleaned high-pressure reaction kettle to a certain temperature, vacuumizing, adjusting the temperature to 50 ℃ after ensuring that the used reaction kettle is completely dried, sealing the reaction kettle, and adding N 2 The gas in the kettle is replaced for a plurality of times, then the ethylene gas is pumped and discharged for a plurality of times, the cyclohexane solvent, the alkyl aluminum cocatalyst c, the pyrrole derivative ligand b, the improver d, the complex a of the main catalyst and the efficiency slow-release agent are injected into the kettle in sequence, and the ethylene is introduced. Continuously reacting for a period of time at a reaction temperature of 120 ℃ and a reaction pressure of 5.0MPa, and feeding a gas-phase product by using a wet gas flowmeter and a gas collecting bag after the reaction is finishedAnd (4) carrying out quantitative collection, collecting liquid-phase products by using a flask, collecting solid-phase products by using a sealed bag, and analyzing and calculating the obtained products respectively.
Example 6
(1) The premixing method of the main catalyst and the efficiency slow-release agent comprises the following steps: taking the cleaned and dried pressure-resistant container, opening a valve, and adding N 2 Adding an efficacy slow-release agent and a main catalyst into the reactor in sequence under protection, wherein the premixed molar ratio of the main catalyst to the efficacy slow-release agent is 1:3, closing a valve, heating to 40 ℃, and supplementing N into the reactor 2 Stirring the mixture for 60min to 0.7MPa, and marking the mixture as a complex a of the main catalyst and the efficacy slow-release agent.
(2) The ethylene trimerization reaction method comprises the following steps: heating the cleaned high-pressure reaction kettle to a certain temperature, vacuumizing, adjusting the temperature to 50 ℃ after ensuring that the used reaction kettle is completely dried, sealing the reaction kettle, and adding N 2 The gas in the kettle is replaced for a plurality of times, then the ethylene gas is pumped and discharged for a plurality of times, the cyclohexane solvent, the alkyl aluminum cocatalyst c, the pyrrole derivative ligand b, the improver d, the complex a of the main catalyst and the efficiency slow-release agent are injected into the kettle in sequence, and the ethylene is introduced. Continuously reacting for a period of time at the reaction temperature of 120 ℃ and the reaction pressure of 5.0MPa, quantitatively collecting gas-phase products by using a wet gas flowmeter and a gas collecting bag after the reaction is finished, collecting liquid-phase products by using a flask, collecting solid-phase products by using a sealing bag, and analyzing and calculating the obtained products respectively.
Example 7
(1) The premixing method of the main catalyst and the efficiency slow-release agent comprises the following steps: taking the cleaned and dried pressure-resistant container, opening a valve, and adding N 2 Adding an efficacy slow-release agent and a main catalyst into the solution in turn under protection, wherein the premixed molar ratio of the main catalyst to the efficacy slow-release agent is 1:5, closing a valve, heating to 40 ℃, and supplementing N into the solution 2 Stirring the mixture for 60min to 0.9MPa, and marking the mixture as a complex a of the main catalyst and the efficacy slow-release agent.
(2) The ethylene trimerization reaction method comprises the following steps: heating the cleaned high-pressure reaction kettle to a certain temperature, then vacuumizing, ensuring that the used reaction kettle is completely dried,adjusting the temperature to 50 ℃, sealing the reaction kettle, and adding N 2 The gas in the kettle is replaced for a plurality of times, then the ethylene gas is pumped and discharged for a plurality of times, the cyclohexane solvent, the alkyl aluminum cocatalyst c, the pyrrole derivative ligand b, the improver d, the complex a of the main catalyst and the efficiency slow-release agent are injected into the kettle in sequence, and the ethylene is introduced. Continuously reacting for a period of time at the reaction temperature of 120 ℃ and the reaction pressure of 5.0MPa, quantitatively collecting gas-phase products by using a wet gas flowmeter and a gas collecting bag after the reaction is finished, collecting liquid-phase products by using a flask, collecting solid-phase products by using a sealing bag, and analyzing and calculating the obtained products respectively.
Example 8
(1) The premixing method of the main catalyst and the efficiency slow-release agent comprises the following steps: taking the cleaned and dried pressure-resistant container, opening a valve, and adding N 2 Adding an efficacy slow-release agent and a main catalyst into the reactor in sequence under protection, wherein the premixed molar ratio of the main catalyst to the efficacy slow-release agent is 1:5, closing a valve, heating to 50 ℃, and supplementing N into the reactor 2 Stirring the mixture for 60min to 0.9MPa, and marking the mixture as a complex a of the main catalyst and the efficacy slow-release agent.
(2) The ethylene trimerization reaction method comprises the following steps: heating the cleaned high-pressure reaction kettle to a certain temperature, vacuumizing, adjusting the temperature to 50 ℃ after ensuring that the used reaction kettle is completely dried, sealing the reaction kettle, and adding N 2 The gas in the kettle is replaced for a plurality of times, then the ethylene gas is pumped and discharged for a plurality of times, the cyclohexane solvent, the alkyl aluminum cocatalyst c, the pyrrole derivative ligand b, the improver d, the complex a of the main catalyst and the efficiency slow-release agent are injected into the kettle in sequence, and the ethylene is introduced. Continuously reacting for a period of time at the reaction temperature of 120 ℃ and the reaction pressure of 5.0MPa, quantitatively collecting gas-phase products by using a wet gas flowmeter and a gas collecting bag after the reaction is finished, collecting liquid-phase products by using a flask, collecting solid-phase products by using a sealing bag, and analyzing and calculating the obtained products respectively.
Example 9
(1) The premixing method of the main catalyst and the efficiency slow-release agent comprises the following steps: taking the cleaned and dried pressure-resistant container, opening a valve, and adding N 2 Is protected downwards toSequentially adding an efficacy slow-release agent and a main catalyst, wherein the premixed molar ratio of the main catalyst to the efficacy slow-release agent is 1:7, closing a valve, heating to 40 ℃, and supplementing N into the mixture 2 Stirring the mixture for 60min to 0.7MPa, and marking the mixture as a complex a of the main catalyst and the efficacy slow-release agent.
(2) The ethylene trimerization reaction method comprises the following steps: heating the cleaned high-pressure reaction kettle to a certain temperature, vacuumizing, adjusting the temperature to 50 ℃ after ensuring that the used reaction kettle is completely dried, sealing the reaction kettle, and adding N 2 The gas in the kettle is replaced for a plurality of times, then the ethylene gas is pumped and discharged for a plurality of times, the cyclohexane solvent, the alkyl aluminum cocatalyst c, the pyrrole derivative ligand b, the improver d, the complex a of the main catalyst and the efficiency slow-release agent are injected into the kettle in sequence, and the ethylene is introduced. Continuously reacting for a period of time at the reaction temperature of 120 ℃ and the reaction pressure of 5.0MPa, quantitatively collecting gas-phase products by using a wet gas flowmeter and a gas collecting bag after the reaction is finished, collecting liquid-phase products by using a flask, collecting solid-phase products by using a sealing bag, and analyzing and calculating the obtained products respectively.
Example 10
(1) The premixing method of the main catalyst and the efficiency slow-release agent comprises the following steps: taking the cleaned and dried pressure-resistant container, opening a valve, and adding N 2 Adding an efficacy slow-release agent and a main catalyst into the reactor in sequence under protection, wherein the premixed molar ratio of the main catalyst to the efficacy slow-release agent is 1:9, closing a valve, heating to 30 ℃, and supplementing N into the reactor 2 Stirring the mixture for 60min to 0.9MPa, and marking the mixture as a complex a of the main catalyst and the efficacy slow-release agent.
(2) The ethylene trimerization reaction method comprises the following steps: heating the cleaned high-pressure reaction kettle to a certain temperature, vacuumizing, adjusting the temperature to 50 ℃ after ensuring that the used reaction kettle is completely dried, sealing the reaction kettle, and adding N 2 The gas in the kettle is replaced for a plurality of times, then the ethylene gas is pumped and discharged for a plurality of times, the cyclohexane solvent, the alkyl aluminum cocatalyst c, the pyrrole derivative ligand b, the improver d, the complex a of the main catalyst and the efficiency slow-release agent are injected into the kettle in sequence, and the ethylene is introduced. Continuously reacting for a period of time at the reaction temperature of 120 ℃ and the reaction pressure of 5.0MPa to obtain a reaction productAnd after the product is finished, quantitatively collecting the gas-phase product by using a wet gas flowmeter and a gas collecting bag, collecting the liquid-phase product by using a flask, collecting the solid-phase product by using a sealing bag, and analyzing and calculating the obtained products respectively.
Comparative example 3
Heating high-pressure reaction kettle to a certain temperature, vacuumizing, regulating the temperature to 50 deg.C after ensuring the reaction kettle is completely dried, sealing the reaction kettle, and adding N 2 Replacing the gas in the kettle for several times, then pumping and discharging ethylene gas for several times, sequentially injecting a cyclohexane solvent, an alkyl aluminum cocatalyst c, a pyrrole derivative ligand b, an improver d and a main catalyst a1 into the kettle, and introducing ethylene. Continuously reacting for a period of time at the reaction temperature of 120 ℃ and the reaction pressure of 5.0MPa, quantitatively collecting gas-phase products by using a wet gas flowmeter and a gas collecting bag after the reaction is finished, collecting liquid-phase products by using a flask, collecting solid-phase products by using a sealing bag, and analyzing and calculating the obtained products respectively.
TABLE 2 results of ethylene trimerization examples and comparative examples are summarized
Claims (10)
1. A method for preparing 1-butene and 1-hexene, wherein the speed of ethylene dimerization and ethylene trimerization is coupled, including the course of shortening the time of ethylene dimerization and producing 1-butene, and the course of increasing the time of ethylene trimerization and producing 1-hexene;
the process for shortening the time of ethylene dimerization to 1-butene comprises the following steps: premixing a cocatalyst and a main catalyst or respectively adding the cocatalyst and the main catalyst into an oligomerization reactor containing a reaction medium, controlling the reaction temperature, introducing an ethylene monomer and keeping the reaction pressure, and carrying out oligomerization to prepare 1-butene; the main catalyst is selected from MX 2 At least one of the metal compounds of (a);
the process for increasing the time for ethylene trimerization to produce 1-hexene comprises: premixing or respectively adding a cocatalyst, a main catalyst, a ligand, an auxiliary agent and an efficiency slow-release agent into an oligomerization reactor containing a reaction medium, controlling the reaction temperature, introducing an ethylene monomer and keeping the reaction pressure, and carrying out oligomerization to prepare 1-hexene; the efficiency slow release agent is at least one selected from silanes, imines and aryl compounds;
wherein the main catalyst is selected from Ti [ OCHR ] 1 CHR 2 CHR 3 O] 2 Wherein R is 1 、R 2 、R 3 Is hydrogen, or is a linear or branched alkyl group of 1 to 20 carbon atoms, or is an aryl group optionally substituted with an alkyl, aryl or aralkyl group containing 2 to 30 carbon atoms, and has the following structural formula:
2. the method of claim 1, wherein the efficiency-retarding agent is one or more of benzene, toluene, ethylbenzene, propylbenzene, 3,3' -dimethylbiphenyl, phenylsilane, 2-ethylaniline, N-ethylaniline, 2-methylbiphenyl, 3-methylbiphenyl, benzyltrimethylsilane, and p-tert-butyltoluene.
3. The method of claim 1, wherein the main catalyst and the efficiency retarder are premixed in advance during the process of increasing the time for generating 1-hexene through the ethylene trimerization reaction.
4. The process for producing 1-butene and 1-hexene as claimed in claim 3, wherein the premixing temperature is 0 to 50 ℃, the premixing pressure is 0 to 2MPa, and the premixing molar ratio of the main catalyst to the efficiency sustained-release agent is 1 (1 to 10).
5. Process for the preparation of 1-butene and 1-hexene according to claim 1, characterized in that said cocatalyst is chosen from one or more of the alkylaluminium compounds chosen from one or more of trimethylaluminium, triethylaluminium, triisobutylaluminium.
6. The process for the production of 1-butene and 1-hexene as claimed in claim 1, wherein the ligand is selected from one or more of pyrrole compounds selected from one or more of pyrrole, 1-methylpyrrole, 2,5-dimethylpyrrole, the auxiliary is selected from one or more of haloalkanes selected from one or more of tetrabromoethane, 1-bromoheptadecafluorooctane, hexachlorocyclohexane.
7. The process for the preparation of 1-butene and 1-hexene as claimed in claim 1, wherein the reaction temperature is 10 to 120 ℃ and the reaction pressure is 1 to 10MPa during the reduction of the time for the dimerization of ethylene to 1-butene.
8. The process for the preparation of 1-butene and 1-hexene as claimed in claim 1, characterized in that during said increasing of the time for the trimerization of ethylene to produce 1-hexene, the reaction temperature is between 30 and 150 ℃ and the reaction pressure is between 1 and 10MPa.
9. The process for preparing 1-butene and 1-hexene according to claim 1, wherein the molar ratio of the cocatalyst to the main catalyst in the process of shortening the time of dimerization of ethylene to 1-butene is (3-15): 1.
10. The method for preparing 1-butene and 1-hexene as claimed in claim 1, wherein the molar ratio of the main catalyst, the ligand, the cocatalyst, the auxiliary agent and the efficiency slow-release agent is 1 (3-6) to (50-150) to (10-20) to (1-10) in the process of increasing the time for trimerization of ethylene to produce 1-hexene.
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| CN1031364A (en) * | 1987-07-13 | 1989-03-01 | 苏联科学院化学物理研究所 | The preparation method of butene-1 |
| US6444867B1 (en) * | 2001-05-17 | 2002-09-03 | Bp Corporation North America Inc. | Process for linear alpha olefins |
| CN105294376A (en) * | 2014-07-04 | 2016-02-03 | Ifp新能源公司 | Improved process for the selective dimerisation of ethylene to 1-butene |
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| CN1031364A (en) * | 1987-07-13 | 1989-03-01 | 苏联科学院化学物理研究所 | The preparation method of butene-1 |
| US6444867B1 (en) * | 2001-05-17 | 2002-09-03 | Bp Corporation North America Inc. | Process for linear alpha olefins |
| CN105294376A (en) * | 2014-07-04 | 2016-02-03 | Ifp新能源公司 | Improved process for the selective dimerisation of ethylene to 1-butene |
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